U.S. patent number 5,206,199 [Application Number 07/860,014] was granted by the patent office on 1993-04-27 for catalyst for polymerizing an olefin and process for polymerizing an olefin.
This patent grant is currently assigned to Mitsui Petrochemical Industries, Ltd.. Invention is credited to Norio Kashiwa, Mamoru Kioka, Akinori Toyota, Toshiyuki Tsutsui.
United States Patent |
5,206,199 |
Kioka , et al. |
April 27, 1993 |
Catalyst for polymerizing an olefin and process for polymerizing an
olefin
Abstract
An olefin is polymerized or copolymerized under the presence of
an olefin-polymerizing catalyst prepared from (A) a
transition-metal compound or (A') a transition-metal compound
loaded on a fine-particle carrier, said transition metal being
selected from group IVB in the periodic table; (B) an aluminoxane;
and (C) an organoaluminum compound represented by the general
formula [I] or [II]: wherein R.sup.1, R.sup.2, and R.sup.3 are
selected from hydrocarbon radicals, R.sup.4 is selected from the
group consisting of hydrocarbon, alkoxy, and aryloxy radicals, and
m and n are positive numbers of 0<m<3 and 0<n<3. This
catalyst has a significantly high polymerization activity, and the
thus produced olefin polymer or copolymer has a narrow composition
distribution, a high bulk density, and uniform grain size with
little powdery product.
Inventors: |
Kioka; Mamoru (Iwakuni,
JP), Kashiwa; Norio (Iwakuni, JP), Tsutsui;
Toshiyuki (Ohtake, JP), Toyota; Akinori (Iwakuni,
JP) |
Assignee: |
Mitsui Petrochemical Industries,
Ltd. (Tokyo, JP)
|
Family
ID: |
27508339 |
Appl.
No.: |
07/860,014 |
Filed: |
March 30, 1992 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
Issue Date |
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290110 |
Dec 16, 1988 |
5122491 |
Jun 16, 1992 |
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Foreign Application Priority Data
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Apr 20, 1987 [JP] |
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62-95445 |
Apr 20, 1987 [JP] |
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62-95446 |
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Current U.S.
Class: |
502/117; 502/103;
526/127; 526/128; 526/129; 526/943 |
Current CPC
Class: |
C08F
10/00 (20130101); C08F 10/00 (20130101); C08F
4/65912 (20130101); C08F 10/00 (20130101); C08F
4/6028 (20130101); C08F 4/65912 (20130101); C08F
4/65916 (20130101); C08F 4/6592 (20130101); Y10S
526/943 (20130101) |
Current International
Class: |
C08F
10/00 (20060101); C08F 4/00 (20060101); C08F
4/6592 (20060101); C08F 4/659 (20060101); C08F
004/642 () |
Field of
Search: |
;502/103,117 |
References Cited
[Referenced By]
U.S. Patent Documents
Foreign Patent Documents
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0131420 |
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Jan 1985 |
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EP |
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2539133 |
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Jul 1984 |
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FR |
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45-20110 |
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Jul 1970 |
|
JP |
|
2057468 |
|
Apr 1981 |
|
GB |
|
Primary Examiner: Garvin; Patrick P.
Attorney, Agent or Firm: Sherman & Shalloway
Parent Case Text
This is a division of application Ser. No. 07/290,110 filed Dec.
16, 1988 and now U.S. Pat. No. 5,122,491, issued Jun. 16, 1992.
Claims
We claim:
1. A catalyst for polymerizing or copolymerizing an olefin, said
catalyst comprising
(A') a supported transition metal compound component consisting
essentially of a transition-metal metallocene compound loaded on a
fine-particle carrier, said transition metal being hafnium,
zirconium or titanium, said transition-metal metallocene compound
having a ligand including conjugated .pi. electron,
(B) an aluminoxane, and
(C) an organoaluminum compound represented by the general formula
(I) or (II):
wherein R.sup.1, R.sup.2, and R.sup.3 are selected from hydrocarbon
radicals, R.sup.4 is selected from the group consisting of
hydrocarbon, alkoxy, and aryloxy radicals, and m and n are positive
numbers of 0<m<3 and 0<n<3.
2. The catalyst according to claim 1 wherein said fine particle
carrier is subjected to preliminary contact treatment with an
organoaluminum compound, aluminoxane compound or halogen-containing
silane compound prior to the loading of the group IVB
transition-metal compound.
3. The catalyst of claim 1 wherein said compound (A) is a compound
represented by the general formula (III):
wherein R.sup.1' is unsubstituted or substituted cycloalkadienyl
radical; R.sup.2', R.sup.3' and R.sup.4' are independently selected
from the group consisting of cycloalkadienyl, aryl, alkyl,
cycloalkyl and aralkyl radicals, halogen atom, hydrogen, OR.sup.a
SR.sup.b, NR.sup.c.sub.2 and PR.sup.d.sub.2, wherein R.sup.a,
R.sup.b, R.sup.c and R.sup.d are hydrocarbon radicals independently
selected from the group consisting of alkyl, cycloalkyl, aryl and
aralkyl radicals and silyl radical, with the proviso that R.sup.c
and R.sup.d may, taken together, form a ring; k'.gtoreq.1; and
k'+l'+m'+n'=4; and R.sup.1' and R.sup.2' may be bonded by an
intervening lower alkylene radical when R.sup.2' is a
cycloalkadienyl radical.
4. The catalyst of claim 1 wherein, in formula (I) or (II),
R.sup.1, R.sup.2 and R.sup.3 are independently selected from the
group consisting of linear or branched, saturated or unsaturated,
aliphatic hydrocarbon radical having 1 to 10 carbon atoms,
alicyclic hydrocarbon radical having 4 to 10 carbon atoms; and
aromatic hydrocarbon radical having 6 to 16 carbon atoms.
5. The catalyst of claim 4 wherein, in formula (I), R.sup.1 is
branched alkyl radical.
6. The catalyst of claim 4 wherein, in formula (I), R.sup.3 is
branched alkyl radical.
7. The catalyst of claim 4 wherein, in formula (I), R.sup.2 is
methyl radical.
8. The catalyst of claim 1 wherein, in formula (I), R.sup.4 is
selected from the group consisting of aliphatic hydrocarbon radical
having 1 to 10 carbon atoms, alicyclic hydrocarbon radical having 4
to 10 carbon atoms, aromatic hydrocarbon radical having 6 to 16
carbon atoms, alkoxy radical having 4 to 10 carbon atoms, and
aryloxy radical.
9. The catalyst of claim 1 wherein the organoaluminum compound (C)
is a compound represented by the formula (I).
10. The catalyst of claim 1 wherein the organoaluminum compound (C)
is a compound represented by the formula (II).
11. The catalyst according to claim 1 wherein the aluminoxane (B)
is represented by formula (VII) or (VIII): ##STR9## wherein R is a
hydrocarbon radical selected from the group consisting of methyl,
ethyl, n-propyl, isopropyl, n-butyl, and isobutyl, and m is an
integer of at least 2.
12. The catalyst according to claim 1 wherein said fine-particle
carrier is an inorganic carrier selected from the group consisting
of SiO.sub.2, Al.sub.2 O.sub.3, MgO, ZrO.sub.2, TiO.sub.2, B.sub.2
O.sub.3, CaO, ZnO, ThO.sub.2, and mixtures thereof.
13. The catalyst according to claim 12 wherein said inorganic
fine-particle carrier has a diameter in the range of from about 10
to 150 .mu.m.
14. The catalyst according to claim 1 wherein said fine-particle
carrier is an organic polymeric carrier selected from the group
consisting of polyolefins, polyesters, polyamides, polyvinyl
chlorides, polystyrene, and natural high polymers.
15. The catalyst according to claim 14 wherein said organic
fine-particle carrier has a diameter in the range of from about 10
to 150 .mu.m.
16. The catalyst according to claim 2 wherein said fine particle
carrier is subject to said preliminary contact treatment with an
aluminoxane compound having the formula (IV) or (V): ##STR10##
wherein R.sup.5 is methyl, ethyl, propyl or butyl, X is chlorine or
bromine, R.sup.6 is R.sup.5 or X, a is a number from 0 to 80, b is
a number from 0 to 80 and the sum of a and b is from 4 to 100.
17. The catalyst according to claim 2 wherein the fine particle
carrier is contacted with from about 0.05 to 30 milligram atoms,
calculated as metal atom, of said organoaluminum, aluminoxane or
silane compound, per gram of the fine-particle carrier.
18. The catalyst according to claim 1 wherein at least a portion of
said aluminoxane catalyst component (B) is also loaded on said
fine-particle carrier.
19. The catalyst according to claim 18 which comprises from about
0.5 to 500 mg atoms, calculated as transition metal atom of the
transition metal compound per 100 g of the fine-particle carrier;
and from about 5 to 50,000 mg atoms, calculated as aluminum atom of
the aluminoxane (B) per 100 g of the fine-particle carrier.
20. The catalyst according to claim 18 which comprises from about 1
to 200 mg atoms, calculated as transition metal atom of the
transition metal compound per 100 g of the fine-particle carrier;
and from about 50 to 100,000 mg atoms, calculated as aluminum atom
of the aluminoxane (B) per 100 g of the fine-particle carrier.
21. The catalyst according to claim 18 which comprises from about 3
to 50 mg atoms, calculated as transition metal atom of the
transition metal compound per 100 g of the fine-particle carrier;
and from about 100 to 4000 mg atoms, calculated as aluminum atom of
the aluminoxane (B) per 100 g of the fine-particle carrier.
22. The catalyst according to claim 19 wherein the ratio of
aluminum atoms contained in (B) to the sum of aluminum atoms
contained in (B) plus (C) is from 20 to 95%.
23. The catalyst according to claim 21 wherein the ratio of
aluminum atoms contained in (B) to the sum of aluminum atoms
contained in (B) plus (C) is from 40 to 92%.
24. The catalyst according to claim 22 wherein the ratio of the sum
of the aluminum atoms in (B) and (C) in the transition metal atoms
in (A) is from 20 to 10,000.
25. The catalyst according to claim 23 wherein the ratio of the sum
of the aluminum atoms in (B) and (C) in the transition metal atoms
in (A) is from 40 to 5000.
26. The catalyst according to claim 1 which further comprises from
about 1 to 1000 g, per gram atom of the transition metal component,
of an olefin polymer polymerized thereon.
27. The catalyst according to claim 1 which further comprises from
about 5 to 500 g, per gram atom of the transition metal component,
of an olefin polymer polymerized thereon.
28. The catalyst according to claim 1 which further comprises from
about 10 to 200 g, per gram atom of the transition metal component,
of an olefin polymer polymerized thereon.
Description
TECHNICAL FIELD
The present invention relates to a catalyst for polymerizing of an
olefin and a process for polymerizing an olefin by using such a
catalyst. More specifically, the present invention relates to a
catalyst and a process for polymerizing a high-molecular weight
olefin at a high polymerization activity even when the amount of
expensive aluminoxane included in the catalyst is reduced. Further,
the present invention relates to a catalyst and a process for
polymerizing an olefin to produce an olefin polymer having a narrow
molecular-weight distribution, and an olefin copolymer having a
narrow composition distribution as well as a narrow
molecular-weight distribution at a high polymerization activity
when applied to the copolymerization of two or more olefins. Still
further, the present invention relates to a catalyst and a process
for polymerizing an olefin to produce an olefin polymer having a
narrow molecular-weight distribution, a high bulk density, and
excellent powder properties.
BACKGROUND TECHNOLOGY
a-olefin polymers, particularly ethylene polymer and an
ethylene-a-olefin copolymer have generally been prepared by a known
process wherein ethylene is polymerized, or ethylene and an
a-olefin are copolymerized under the presence of a titanium-based
catalyst comprising a titanium compound and an organoaluminum
compound or a vanadium-based catalyst comprising a vanadium
compound and an organoaluminum compound.
A new series of Ziegler catalysts comprising a zirconium compound
and an aluminoxane have also been recently proposed for
polymerization of an olefin.
Japanese Patent Application Kokai No. 58-19309 describes a process
for polymerizing ethylene and at least one C.sub.3 -C.sub.12
a-olefin at a temperature of from -50.degree. to 200.degree. C.
under the presence of a catalyst comprising a transition
metal-containing compound represented by the formula:
wherein R is selected from cyclopentadienyl, C.sub.1 -C.sub.6
alkyl, and halogen, Me is a transition metal, and Hal is a
halogen,
a linear aluminoxane represented by the formula:
wherein R is methyl or ethyl, and n is a number of 4 to 20, and
a cyclic aluminoxane represented by the formula: ##STR1## wherein R
and n are as defined above. It is also described that ethylene
should be polymerized in the presence of a small amount, that is,
up to 10% by weight of an a-olefin having a somewhat longer chain
or the mixture thereof to adjust a density of the resulting
polyethylene.
Japanese Patent Application Kokai No. 59-95292 describes processes
for preparing a linear aluminoxane represented by the formula:
##STR2## wherein n is a number of 2 to 40 and R is a C.sub.1
-C.sub.6 alkyl, and a cyclic aluminoxane represented by the
formula: ##STR3## wherein n and R are as described above. It is
also disclosed that at least 25 million grams of polyethylene may
be produced per 1 g of transition metal per hour when an olefin is
polymerized in the presence of a mixture of, for example,
methylaluminoxane prepared as described above and a
bis(cyclopentadienyl) compound containing titanium or
zirconium.
Japanese Patent Application Kokai 60-35005 discloses a process for
preparing an olefin-polymerization catalyst comprising effecting a
reaction between a magnesium compound and an aluminoxane compound
represented by the formula: ##STR4## wherein R.sup.1 is a C.sub.1
-C.sub.10 alkyl radical, and R.sup.0 may represent R.sup.1 or,
taken together, form --O--; chlorinating the reaction product; and
treating the product with Ti, V, Zr, or Cr-containing compound to
produce an olefin-polymerizing catalyst. It is also disclosed that
this catalyst is particularly preferable for copolymerizing
ethylene with a C.sub.3 -C.sub.12 a-olefin.
Japanese Patent Application Kokai No. 60-35006 discloses a catalyst
system for polymers blended in a reactor which comprises a
combination of (a) a mono-, di- or tri-cyclopentadienyl compound of
at least two different transition metals, or a derivative thereof,
and (b) an aluminoxane. Example 1 of this application discloses
that a polyethylene having a number average molecular weight of
15,300, a weight average molecular weight of 36,400, and propylene
content of 3.4% may be prepared by polymerizing ethylene and
propylene by using bis(pentamethylcyclopentadienyl)zirconium
dimethyl and an aluminoxane as catalyst. Example 2 discloses that a
blend of polyethylene and ethylene-propylene copolymer having a
number average molecular weight of 2,000, a weight average
molecular weight of 8,300, and propylene content of 7.1 mol % and
comprising a toluene-soluble portion having a number average
molecular weight of 2,200, a weight average molecular weight of
11,900, and propylene content of 30 mol % and a toluene-insoluble
portion having a number average molecular weight of 3,000, a weight
average molecular weight of 7,400, and propylene content of 4.8 mol
% may be prepared by polymerizing ethylene and propylene by using
bis(pentamethylcyclopentadienyl)zirconium dichloride,
bis(methylcyclopentadienyl)zirconium dichloride, and an aluminoxane
as catalyst. Example 3 discloses a blend of LLDPE and
ethylene-propylene copolymer comprising a soluble portion having a
molecular weight distribution (Mw/Mn) of 4.57 and propylene content
of 20.6 mol %, and an insoluble portion having a molecular weight
distribution of 3.04 and propylene content of 2.9 mol %.
Japanese Patent Application Kokai No. 60-35007 describes a process
for polymerizing ethylene either alone or together with an a-olefin
having at least 3 carbon atoms under the presence of a catalyst
containing a metallocene and a cyclic aluminoxane represented by
the formula: ##STR5## wherein R is an alkyl radical of 1 to 5
carbon atoms and n is as described above. The polymer prepared by
such a process has a weight average molecular weight of about 500
to about 1,400,000 and a molecular-weight distribution of 1.5 to
4.0.
Japanese Patent Application Kokai No. 60-35008 discloses that a
polyethylene or an ethylene-C.sub.3-10 a-olefin copolymer having a
wide molecular-weight distribution may be prepared by using a
catalyst system containing at least two metallocenes and an
aluminoxane. There is also disclosed that the copolymer has a
molecular-weight distribution (Mw/Mn) of 2 to 50.
Japanese Patent Application Kokai Nos. 60-260602 and 60-130604
disclose processes for polymerizing an olefin by utilizing
catalysts comprising a transition metal compound and mixed
organoaluminum compound of an aluminoxane and organoaluminum
compound. These patent applications disclose that polymerization
activity per unit weight of the transition metal can be increased
by adding the organoaluminum compound. However, these processes
suffered from a defect that the catalysts required a large amount
of expensive aluminoxane, and the activity per unit weight of the
aluminoxane was still low.
The catalysts comprising a transition metal compound and an
aluminoxane as proposed in the above-mentioned patent applications
are provided with a significantly superior polymerization activity
compared to the conventional catalyst systems prepared from a
transition metal compound and an organoaluminum compound. These
catalysts, however, are mostly soluble in the reaction system, and
frequently require adoption of solution polymerization system,
resulting in a significantly increased viscosity of the
polymerization-system solution. Moreover, the polymers produced by
subsequently treating with these solution systems have low bulk
density, and therefore, polymers having excellent powder properties
have been quite difficult to obtain.
On the other hand, attempts have been made to polymerize an olefin
in dispersion or gas-phase polymerization systems by using
catalysts wherein one or both of said transition metal compound and
said aluminoxane are supported on a porous carrier of an inorganic
oxide such as silica, silica-alumina, and alumina.
For example, aforementioned Japanese Patent Application Kokai Nos.
60-35006, 60-35007 and 60-35008 disclose that the transition metal
compound and the aluminoxane supported on a carrier such as silica,
silica-alumina, and alumina can also be used as catalysts.
Japanese Patent Application Kokai Nos. 60-106808 and 61-106809
disclose a process for preparing a composition comprising a
polyethylene-based polymer and a filler which involves
preliminarily contacting a high-activity catalyst component
containing titanium and/or zirconium which is soluble in a
hydrocarbon solvent with a filler, and then polymerizing ethylene
or copolymerizing ethylene and an a-olefin in the presence of the
thus treated catalyst component, an organoaluminum compound, and a
filler which has an affinity for a polyolefin.
Japanese Patent Application Kokai No. 61-31404 discloses a process
for polymerizing ethylene or copolymerizing ethylene and an
a-olefin in the presence of a mixed catalyst comprising a
transition metal compound and a product obtained by reacting a
trialkylaluminum and water under the presence of silicon dioxide or
aluminum oxide.
Japanese Patent Application Kokai No. 61-276805 discloses a process
for polymerizing an olefin in the presence of a catalyst comprising
a reaction mixture between an inorganic oxide containing surface
hydroxyl radical such as silica and a reaction mixture obtained by
reacting a zirconium compound and an aluminoxane with a
trialkylaluminum.
Japanese Patent Application Kokai Nos. 60-108610 and 61-296008
discloses a process for polymerizing an olefin in the presence of a
catalyst comprising a transition metal compound such as a
metallocene and an aluminoxane supported on a carrier such as an
inorganic oxide.
However, when an olefin is polymerized or copolymerized in a
dispersion or gas-phase polymerization system by utilizing the
solid catalyst components supported on a carrier as mentioned
above, polymerization activity is markedly reduced and the
properties inherent to the catalyst comprising the transition metal
compound catalyst component and the aluminoxane catalyst component
are not fully exerted. Powder properties such as bulk density of
the thus prepared polymer were also insufficient.
SUMMARY OF THE INVENTION
An object of the present invention is to provide a catalyst which
can polymerize an olefin at a high polymerization activity per
aluminoxane contained in the catalyst and produce a high-molecular
weight olefin polymer having a narrow molecular-weight distribution
or a high-molecular weight olefin copolymer, particularly an
ethylene a-olefin copolymer, having both narrow molecular-weight
distribution and composition distribution when used in the
copolymerization of two or more olefins. Another object of the
present invention is to provide a method for polymerizing an olefin
by using such a catalyst.
Further object of the present invention is to provide a catalyst
which can polymerize an olefin at a high polymerization activity
and produce an olefin polymer having a high bulk density and
excellent powder properties. A still further object of the present
invention is to provide a method for polymerizing an olefin polymer
by using such a catalyst.
According to the present invention, there are provided a catalyst
prepared from
(A) a transition-metal compound, said transition metal being
selected from group IVB in the periodic table,
(B) an aluminoxane, and
(C) an organoaluminum compound represented by the general formula
[I] or [II]:
wherein R.sup.1, R.sup.2, and R.sup.3 are selected from hydrocarbon
radicals, R.sup.4 is selected from the group consisting of
hydrocarbon, alkoxy, and aryloxy radicals, and m and n are each a
positive number of 0<m<3 and 0<n<3; and a process for
polymerizing an olefin wherein the olefin is polymerized or
copolymerized in the presence of said catalyst.
According to the present invention, there are each also provided a
catalyst prepared from
(A') a transition-metal compound supported on a fine-particle
carrier, said transition metal being selected from group IVB in the
periodic table,
(B) an aluminoxane, and
(C) an organoaluminum compound represented by the general formula
[I] or [II]:
wherein R.sup.1, R.sup.2, and R.sup.3 are selected from hydrocarbon
radicals, R.sup.4 is selected from the group consisting of
hydrocarbon, alkoxy, and aryloxy radicals, and m and n are positive
number of 0<m<3 and 0<n<3; and a process for
polymerizing an olefin wherein the olefin is polymerized or
copolymerized in the presence of said catalyst.
DETAILED DESCRIPTION OF THE INVENTION
The term polymerization used herein may include not only
homopolymerization but also copolymerization. Similarly, the term
polymer may include both homopolymer and copolymer.
A catalyst employed in a first embodiment of the present invention
is prepared from three catalyst components (A), (B) and (C).
A group IVB transition metal contained in the catalyst component
(A) is selected from the group consisting of titanium, zirconium
and hafnium. The transition metal contained in the catalyst
component (A) may preferably be titanium or zirconium, and most
preferably is zirconium.
The group IVB transition-metal compound of the catalyst component
(A) may typically be a zirconium compound having a radical
containing conjugated .pi. electron as a ligand.
The zirconium compound having a radical containing conjugated .pi.
electron as a ligand is, for example, a compound represented by the
formula [III]:
wherein R.sup.1 is an unsubstituted or substituted cycloalkadienyl
radical; R.sub.2, R.sub.3 and R.sub.4 are selected from the group
consisting of cycloalkadienyl, aryl, alkyl, cycloalkyl and aralkyl
radicals, halogen atom, hydrogen, OR.sup.a, SR.sup.b,
NR.sup.c.sub.2 and PR.sup.d.sub.2, wherein R.sup.a, R.sup.b,
R.sup.c and R.sup.d are hydrocarbon radicals selected from the
group consisting of alkyl, cycloalkyl, aryl and aralkyl radicals or
silyl radicals, with the proviso that R.sup.c and R.sup.d may,
taken together, form a ring; k.gtoreq.1; and k+l+m+n=4. When
R.sup.2 is an cycloalkadienyl radical, R.sup.1 and R.sup.2 may be
bonded by an intervening lower alkylene radical. Examples of the
cycloalkadienyl radicals include cyclopentadienyl,
methylcyclopentadienyl, ethylcyclopentadienyl,
pentamethylcyclopentadienyl, dimethylcyclopentadienyl, indenyl,
tetrahydroindenyl, etc. Examples of the alkyl radicals include
methyl, ethyl, propyl, isopropyl, butyl, hexyl, octyl,
2-ethylhexyl, decyl, oleyl, etc. Examples of the aryl radicals
include phenyl, tolyl, etc. Examples of the aralkyl radicals
include benzyl, neophyl, etc. Examples of the cycloalkyl radicals
include cyclopentyl, cyclohexyl, cyclooctyl, norbonyl,
bicyclononyl, and an alkyl-substituted radical thereof. Examples of
the silyl radicals include trimethylsilyl, triethylsilyl,
phenyldimethylsilyl, triphenylsilyl, etc. Unsaturated aliphatic
radicals such as vinyl, allyl, propenyl, isopropenyl, and
1-butenyl, and unsaturated cycloaliphatic radicals such as
cyclohexenyl may also be employed. Examples of the halogen atoms
include fluorine, chlorine, bromine, etc. Examples of the lower
alkylene radicals include methylene, ethylene, propylene, butylene,
etc.
Examples of the zirconium compounds include:
bis(cyclopentadienyl)zirconium monochloride monohydride;
bis(cyclopentadienyl)zirconium monobromide monohydride;
bis(cyclopentadienyl)methylzirconium hydride;
bis(cyclopentadienyl)ethylzirconium hydride;
bis(cyclopentadienyl)cyclohexylzirconium hydride;
bis(cyclopentadienyl)phenylzirconium hydride;
bis(cyclopentadienyl)benzylzirconium hydride;
bis(cyclopentadienyl)neopentylzirconium hydride;
bis(methylcyclopentadienyl)zirconium monochloride monohydride;
bis(indenyl)zirconium monochloride monohydride;
bis(cyclopentadienyl)zirconium dichloride;
bis(cyclopentadienyl)zirconium dibromide;
bis(cyclopentadienyl)methylzirconium monochloride;
bis(cyclopentadienyl)ethylzirconium monochloride;
bis(cyclopentadienyl)cyclohexylzirconium monochloride;
bis(cyclopentadienyl)phenylzirconium monochloride;
bis(cyclopentadienyl)benzylzirconium monochloride;
bis(methylcyclopentadienyl)zirconium dichloride;
bis(tetramethylcyclopentadienyl)zirconium dichloride;
bis(indenyl)zirconium dichloride;
bis(indenyl)zirconium dibromide;
bis(cyclopentadienyl)zirconium diphenyl;
bis(cyclopentadienyl)zirconium dibenzyl;
bis(cyclopentadienyl)methoxyzirconium chloride;
bis(cyclopentadienyl)ethoxyzirconium chloride;
bis(cyclopentadienyl)butoxyzirconium chloride;
bis(cyclopentadienyl)-2-ethylhexoxyzirconium chloride;
bis(cyclopentadienyl)methylzirconium ethoxide;
bis(cyclopentadienyl)methylzirconium butoxide;
bis(cyclopentadienyl)ethylzirconium ethoxide;
bis(cyclopentadienyl)phenylzirconium ethoxide;
bis(cyclopentadienyl)benzylzirconium ethoxide;
bis(methylcyclopentadienyl)ethoxyzirconium chloride;
bis(indenylethoxy)zirconium chloride;
bis(cyclopentadienyl)ethoxyzirconium chloride;
bis(cyclopentadienyl)butoxyzirconium chloride;
bis(cyclopentadienyl)-2-ethylhexoxyzirconium chloride;
bis(cyclopentadienyl)phenoxyzirconium chloride;
bis(cyclopentadienyl)cyclohexoxyzirconium chloride;
bis(cyclopentadienyl)phenylmethoxyzirconium chloride;
bis(cyclopentadienyl)methylzirconium phenylmethoxide;
bis(cyclopentadienyl)trimethylsiloxyzirconium chloride;
bis(cyclopentadienyl)triphenylsiloxyzirconium chloride;
bis(cyclopentadienyl)thiophenylzirconium chloride;
bis(cyclopentadienyl)thioethylzirconium chloride;
bis(cyclopentadienyl)bis(dimethylamide)zirconium;
bis(cyclopentadienyl)diethylamidezirconium chloride;
ethylenebis(indenyl)ethoxyzirconium chloride;
ethylenebis(4,5,6,7-tetrahydro-1-indenyl)ethoxy-zirconium
chloride;
ethylenebis(indenyl)dimethylzirconium;
ethylenebis(indenyl)diethylzirconium;
ethylenebis(indenyl)diphenylzirconium;
ethylenebis(indenyl)dibenzylzirconium;
ethylenebis(indenyl)methylzirconium monobromide;
ethylenebis(indenyl)ethylzirconium monochloride;
ethylenebis(indenyl)benzylzirconium monochloride;
ethylenebis(indenyl)methylzirconium monochloride;
ethylenebis(indenyl)zirconium dichloride;
ethylenebis(indenyl)zirconium dibromide;
ethylenebis(4,5,6,7-tetrahydro-1-indenyl)dimethylzirconium;
ethylenebis(4,5,6,7-tetrahydro-1-indenyl)methylzirconium
monochloride;
ethylenebis(4,5,6,7-tetrahydro-1-indenyl)zirconium dichloride;
ethylenebis(4,5,6,7-tetrahydro-1-indenyl)zirconium dibromide;
ethylenebis(4-methyl-1-indenyl)zirconium dichloride;
ethylenebis(5-methyl-1-indenyl)zirconium dichloride;
ethylenebis(6-methyl-1-indenyl)zirconium dichloride;
ethylenebis(7-methyl-1-indenyl)zirconium dichloride;
ethylenebis(5-methoxy-1-indenyl)zirconium dichloride;
ethylenebis(2,3-dimethyl-1-indenyl)zirconium dichloride;
ethylenebis(4,7-dimethyl-1-indenyl)zirconium dichloride;
ethylenebis(4,7-dimethoxy-1-indenyl)zirconium dichloride;
ethylenebis(indenyl)zirconium dimethoxide;
ethylenebis(indenyl)zirconium diethoxide;
ethylenebis(indenyl)methoxyzirconium chloride;
ethylenebis(indenyl)ethoxyzirconium chloride;
ethylenebis(indenyl)methylzirconium ethoxide;
ethylenebis(4,5,6,7-tetrahydro-1-indenyl)zirconium dimethoxide;
ethylenebis(4,5,6,7-tetrahydro-1-indenyl)zirconium ethoxide;
ethylenebis(4,5,6,7-tetrahydro-1-indenyl)methoxyzirconium
chloride;
ethylenebis(4,5,6,7-tetrahydro-1-indenyl)ethoxyzirconium chloride;
and
ethylenebis(4,5,6,7-tetrahydro-1-indenyl)methylzirconium
ethoxide.
Examples of the titanium compound include:
bis(cyclopentadienyl)titanium monohydride monohalide;
bis(cyclopentadienyl)methyltitanium hydride;
bis(cyclopentadienyl)phenyltitanium chloride;
bis(cyclopentadienyl)benzyltitanium chloride;
bis(cyclopentadienyl)titanium dichloride;
bis(cyclopentadienyl)titanium dibenzyl;
bis(cyclopentadienyl)ethoxytitanium chloride;
bis(cyclopentadienyl)butoxytitanium chloride;
bis(cyclopentadienyl)methyltitanium ethoxide;
bis(cyclopentadienyl)phenoxytitanium chloride;
bis(cyclopentadienyl)trimethylsiloxytitanium chloride;
bis(cyclopentadienyl)thiophenyltitanium chloride;
bis(cyclopentadienyl)bis(dimethylamide)titanium;
bis(cyclopentadienyl)diethoxytitanium;
ethylenebis(indenyl)titanium dichloride; and
ethylenebis(4,5,6,7-tetrahydro-1-indenyl)titanium dichloride.
Examples of the hafnium compound include:
bis(cyclopentadienyl)hafnium monochloride monohydride;
bis(cyclopentadienyl)ethylhafnium hydride;
bis(cyclopentadienyl)phenylhafnium chloride;
bis(cyclopentadienyl)hafnium dichloride;
bis(cyclopentadienyl)hafnium dibenzyl;
bis(cyclopentadienyl)ethoxyhafnium chloride;
bis(cyclopentadienyl)butoxyhafnium chloride;
bis(cyclopentadienyl)methylhafnium ethoxide;
bis(cyclopentadienyl)phenoxyhafnium chloride;
bis(cyclopentadienyl)thiophenylhafnium chloride;
bis(cyclopentadienyl)bis(diethylamide)hafnium;
ethylenebis(indenyl)hafnium dichloride; and
ethylenebis(4,5,6,7-tetrahydro-1-indenyl)hafnium dichloride.
The catalyst component (B) is an aluminoxane.
The aluminoxane which can be used herein may be represented by the
formulae [VII] and [VIII]: ##STR6## wherein R is a hydrocarbon
radical selected from the group consisting of methyl, ethyl,
n-propyl, isopropyl, n-butyl, and isobutyl, preferably methyl,
ethyl, or isobutyl, and most preferably methyl; and m is an integer
of at least 2, and preferably at least 5.
The aluminoxane of formulae [VII] and [VIII] may be a halogenated
aluminoxane wherein R may partly be substituted with a halogen atom
such as chlorine and bromine with the proviso that the halogen
content is up to 40% by weight. R may also partly be hydroxyl,
alkoxy and/or aryloxy radical.
Typical processes for preparing said aluminoxane include: (1) a
process comprising preparing a hydrocarbon medium suspension of a
compound containing adsorbed water or a salt containing water of
crystallization such as hydrated magnesium chloride, hydrated
copper sulfate, hydrated aluminum sulfate, hydrated nickel sulfate,
and hydrated cerous chloride; and adding a trialkylaluminum into
said suspension for reaction; and (2) a process wherein water is
directly reacted with a trialkylaluminum in a medium such as
benzene, toluene, ethylether, and tetrahydrofuran.
Among these processes, process (1) is more preferable. A small
amount of organometallic component may also be contained in the
aluminoxane. For example, an organometallic compound such as a
halogen-containing organoaluminum compound and organomagnesium
compound may also be present with the trialkylaluminum.
The component (C) of the catalyst according to the present
invention is an organoaluminum compound represented by the general
formulae [I] and [II]:
wherein R.sup.1, R.sup.2, and R.sup.3 are selected from
hydrocarbons, R.sup.4 is selected from the group consisting of
hydrocarbon, alkoxy, and aryloxy radicals, and m and n are
0<m<3 and 0<n<3. In the organoaluminum compound
represented by the general formulae [I] and [II], R.sup.1, R.sup.2,
and R.sup.3 may typically be a linear or branched, saturated or
unsaturated, aliphatic hydrocarbon radical having 1 to 10 carbon
atoms such as methyl, ethyl, n-propyl, isopropyl, n-butyl, t-butyl,
sec-butyl, isobutyl, n-hexyl, n-octyl, and 2-ethylhexyl; an
alicyclic hydrocarbon radical having 4 to 10 carbon atoms such as
cyclohexane, methylcyclopentyl, and methylcyclohexyl; or an
aromatic hydrocarbon radical having 6 to 16 carbon atoms such as
phenyl, tolyl, xylyl, and naphtyl. In the organoaluminum compound
represented by the general formulae [I] and [II], R.sup.1 and
R.sup.3 may preferably be a branched hydrocarbon radical, and most
preferably is a branched alkyl radical. R.sup.2 may most preferably
a methyl radical. In the organoaluminum compound represented by the
general formula [II], R.sup.4 may typically be an aliphatic
hydrocarbon radical having 1 to 10 carbon atoms such as methyl,
ethyl, propyl, isopropyl, n-butyl, and isobutyl; an alicyclic
hydrocarbon radical having 4 to 10 carbon atoms such as cyclohexyl,
methylcyclopentyl, and methylcyclohexyl; an aromatic hydrocarbon
radical having 6 to 16 carbon atoms such as phenyl, tolyl, xylyl,
and naphtyl; an alkoxy radical having 4 to 10 carbon atoms such as
methoxy, ethoxy, propoxy, butoxy, iso-butoxy, cycloherloxy,
methylcyclopentyloxy, and methylcyclohexyloxy; and an aryloxy
radical such as phenoxy, tolyloxy, and naphthoxy. In the formula
[I], m may be a positive number of 0<m<3, preferably a
positive number of 1<m<2.5, and most preferably m=2. In the
formula [II], n may be a positive number of 0<n<3, preferably
be a positive number of 1<n<2.5, and most preferably be n=
2.
Typical organoaluminum compounds (C) represented by the general
formula [I] include dialkylaluminum alkoxides such as
diethylaluminum methoxide, diisopropylaluminum methoxide,
diisobutylaluminum methoxide, diisobutylaluminum methoxide,
bis(2-methylbutyl)aluminum methoxide, bis(3-methylbutyl)aluminum
methoxide, bis(3-methylbutyl)aluminum methoxide,
bis(2-methylpentyl)aluminum methoxide, bis(3-methylpentyl)aluminum
ethoxide, bis(4-methylpentyl)aluminum propoxide,
bis(2-methylhexyl)aluminum butoxide, and bis(3-methylhexyl)aluminum
cyclohexyloxide; dicycloalkylaluminum alkoxides such as
bis(2-ethylhexyl)aluminum phenoxide, and dicyclohexylaluminum
methoxide; bisarylaluminum alkoxides such as diphenylaluminum
methoxide and bistolylaluminum methoxide; alkylaluminum dialkoxides
such as ethylaluminum dimethoxide, isopropylaluminum dimethoxide,
isobutylaluminum diethoxide, 2-methylbutylaluminum dimethoxide,
3-methylbutylaluminum dimethoxide, 2-methylpentylaluminum
dimethoxide, 3-methylpentylaluminum dimethoxide,
4-methylpentylaluminum dimethoxide, 2-methylhexylaluminum
dipropoxide, 3-methylhexylaluminum dicyclohexyloxide, and
2-ethylhexylaluminum diphenoxide; cycloalkylaluminum dialkoxides
such as cyclohexylaluminum dimethoxide and cyclooctylaluminum
diethoxide; arylaluminum alkoxides such as phenylaluminum methoxide
and tolylaluminum ethoxide; and alkylaluminum sesquialkoxides
wherein the number m equals 1.5 in the above-mentioned
organoaluminum compounds. Among these organoaluminum compounds,
dialkylaluminum alkoxides are preferred, and diisoalkylaluminum
alkoxides are most preferred.
Typical organoaluminum compounds (C) represented by the general
formula [II] include:
The organoaluminum compound (C) may be added to the reaction system
as raw compounds which will react to produce the organoaluminum
compound (C) in the reaction system.
In the process according to the present invention, the catalyst is
generally prepared from the transition-metal compound (A), the
aluminoxane (B), and the organoaluminum compound (C), although any
additional components such as an electron donor may optionally be
added to the reaction system. The electron donor component may be
supplied to the polymerization reaction system either directly with
the transition-metal compound (A), the aluminoxane (B), and the
organoaluminum compound (C), or as a complex or a reaction product
with any of the components (A), (B) and (C). Exemplary electron
donors include carboxylic acids, esters, ethers, ketones,
aldehydes, alcohols, phenols, acid amides, oxygen-containing
compounds such as those containing a metal-O-C bond, the metal
being aluminum, silicon, etc., nitriles, amines, phosphines, etc.
The proportion of the electron donor may generally be from 0 to 1
mole per 1 gram atom of the transition metal element (M).
In the process according to the present invention, catalyst
components (A), (B), and (C) may either be introduced into the
reaction system separately, or two of the components may
preliminarily be contacted before introducing into the reaction
system separately from the remaining one component. Further, all
three components may preliminarily be contacted and then introduced
into the reaction system.
When catalyst components (A) and (B) are subjected to the
preliminary contact process, the concentration of the transition
metal is generally in the range of 2.5.times.10.sup.-4 to
1.5.times.10.sup.-1 gram atoms/liter, and preferably
5.0.times.10.sup.-4 to 1.0.times.10.sup.-1 gram atoms/liter, and
the concentration of the aluminoxane is generally in the range of
from 0.05 to 5 gram atoms/liter and preferably from 0.1 to 3 gram
atoms/liter calculated as aluminum atom. The temperature of the
preliminary contact treatment is generally -50.degree. to
100.degree. C., and the mixing time is generally 0.1 to 50
minutes.
A catalyst employed in a second embodiment of the present invention
is prepared from a solid catalyst component (A'), and catalyst
components (B) and (C).
The solid catalyst component (A') used in the method of the present
invention is a solid component wherein at least a group IVB
transition metal compound is loaded on a fine-particle carrier.
Most preferably, the solid catalyst component is a fine-particle
carrier loaded with the group IVB transition metal compound as well
as the aluminoxane component (B) to allow production of an
excellent olefin polymer having a high bulk density and good powder
properties at an improved polymerization activity.
The carrier constituting the solid catalyst component (A') is a
fine-particle carrier which may be either inorganic or organic.
Examples of the inorganic fine-particle carriers include SiO.sub.2,
Al.sub.2 O.sub.3, MgO, ZrO.sub.2, TiO.sub.2, B.sub.2 O.sub.3, CaO,
ZnO, ThO.sub.2, etc. and mixtures thereof such as SiO.sub.2 --MgO,
SiO.sub.2 --Al.sub.2 O.sub.3, SiO.sub.2 --TiO.sub.2, SiO.sub.2
--V.sub.2 O.sub.5, SiO.sub.2 --Cr.sub.2 O.sub.3, SiO.sub.2
--TiO.sub.2 --MgO, etc. These inorganic fine-particle carriers are
generally calcined at 150.degree. to 1000.degree. C., and
preferably at 200.degree. to 800.degree. C. Among these carriers, a
carrier primarily comprising at least one component selected from
the group consisting of SiO.sub.2 and Al.sub.2 O.sub.3 is
preferred. The inorganic fine-particle carrier may also contain a
minor amount of carbonate such as Na.sub.2 CO.sub.3, K.sub.2
CO.sub.3, CaCO.sub.3, and MgCO.sub.3, sulfates such as Na.sub.2
SO.sub.4, Al.sub.2 (SO.sub.4).sub.3, and BaSO.sub.4, nitrates such
as KNO.sub.3, Mg(NO.sub.3).sub.2 , and Al(NO.sub.3).sub.3, oxides
such as Na.sub.2 O, K.sub.2 O, and Li.sub.2 O, and the like.
Although the inorganic carrier may have different diameters
depending on the type and process of manufacture, the diameter of
the carrier which is preferably utilized in the present invention
is generally 5 to 200 .mu.m, and preferably 10 to 150 .mu.m, and
more preferably 20 to 100 .mu.m.
Examples of the organic fine-particle carriers include polyolefins
such as polyethylene, polypropylene, poly(1-butene),
poly(4-methyl-1-pentene) and those prepared by copolymerizing the
monomers employed for producing such polyolefins; polyesters such
as polymethyl methacrylate, and polymethyl acrylate; polyamides;
polyvinyl chlorides; polystyrene; natural high polymers; and
monomer compounds. Although the properties of the carrier may vary
depending on the type and the process of manufacture, the carrier
which is preferably used in the present invention may have a
diameter of 5 to 500 .mu.m, preferably 10 to 150 .mu.m, and more
preferably 20 to 100 .mu.m.
The carrier may have any molecular weight so long as the carrier
can remain a solid material. For example, a polyester carrier which
may be employed herein has a weight average molecular weight of
from about 1,000 to about 10,000,000.
The fine-particle carrier may be subjected to a preliminary contact
treatment with compounds such as an organoaluminum compound,
aluminoxane compound or halogen-containing silane compound prior to
the loading of the group IVB transition metal compound onto the
carrier.
The organoaluminum compounds which may be used in the preliminary
contact treatment include trialkylaluminums such as
trimethylaluminum, triethylaluminum, tri-n-butylaluminum,
triisobutylaluminum, etc,; alkenylaluminums such as
isoprenylaluminum; dialkylaluminum alkoxides such as
dimethylaluminum methoxide, diethylaluminum ethoxide,
dibutylaluminum butoxide, diisobutylaluminum methoxide, etc.;
alkylaluminum sesquialkoxides such as methylaluminum
sesquimethoxide, ethylaluminum sesquiethoxide, etc.; partially
alkoxylated alkylaluminums having average composition represented
by the formula: R'.sub.2.5 Al(OR").sub.0.5 ; partially halogenated
alkylaluminums, for example, dialkylaluminum halides such as
dimethylaluminum chloride, diethylaluminum chloride,
dimethylaluminum bromide, etc.; alkylaluminum sesquihalides such as
methylaluminum sesquichloride, ethylaluminum sesquichloride, etc.;
and alkylaluminum dihalides such as methylaluminum dichloride,
ethylaluminum dichloride, etc. The organoaluminum compound may
preferably be trialkylaluminum, dialkylaluminum chloride, and
dialkylaluminum alkoxide, and most preferably be trimethylaluminum,
triethylaluminum, triisobutylaluminum, dimethylaluminum chloride,
diethylaluminum chloride, and diisobutylaluminum methoxide. The
aluminoxane compound which may be used in the preliminary contact
treatment of the fine-particle carrier is the one represented by
the general formulae [IV] and [V]: ##STR7## wherein R.sup.5 is a
hydrocarbon radical such as methyl, ethyl, propyl, butyl, and
preferably methyl or ethyl, and most preferably methyl; and X is a
halogen atom such as chlorine and bromine; R.sup.6 is either the
hydrocarbon radical of R.sup.5 or a halogen atom as defined above;
a is a number of 0 to 80, and preferably from 0 to 30; b is a
number of 0 to 80, and preferably from 0 to 30; and the sum of a
and b is from 4 to 100, preferably from 8 to 50. In general
formulae: [IV] and [V], units ##STR8## may either be
block-polymerized, or regularly or irregularly
random-polymerized.
The halogen-containing silane compound which may be used in the
preliminary contact treatment of the fine-particle carrier is an
organoaluminum compound represented by the general formula
[VI]:
wherein X is Cl or Br, R.sup.7 and R.sup.8 are hydrogen atom or
C.sub.1-12 alkyl, aryl, or C.sub.3-12 cycloalkyl, c is a number of
1 to 4, d is a number of 1 to 3, and the sum of c and d is 1 to
4.
Examples of the halogen-containing silane compound include
tetrachlorosilane, tetrabromosilane, trichlorosilane,
trichloromethylsilane, trichloroethylsilane, trichloropropylsilane,
trichlorophenylsilane, trichlorocyclohexylsilane, tribromosilane,
tribromoethylsilane, dichlorodimethylsilane, dichloromethylsilane,
dichlorophenylsilane, trichloromethoxysilane,
trichloroethoxysilane, trichloropropoxysilane,
trichlorophenoxysilane, tribromoethoxysilane,
dichloromethoxysilane, dichlorodimethoxysilane, trichlorosilanol,
etc. A mixture of any of these silane compounds may also be
utilized. Preferred silane compounds are tetrachlorosilane,
trichlorosilane, and trichloromethylsilane.
Other compounds which may be utilized in the preliminary contact
treatment of the fine-particle carrier include organoboron,
organomagnesium, organotin, organolithium etc.
In the preliminary contact treatment of the fine-particle carrier
with the organometallic compound or the silane compound, amount of
the organometallic compound or the silane compound employed may
range from 0.01 to 50, preferably from 0.05 to 30, and most
preferably from 0.1 to 20 milligram atoms calculated as metal atom
per gram of the fine-particle carrier. The treatment is carried out
by adding at least one organometallic compound or silane compound
to the fine-particle carrier dispersed in an inert medium, and the
dispersion is heated to a temperature in the range of from
0.degree. to 120.degree. C., preferably from 10.degree. to
100.degree. C., and more preferably from 20.degree. to 90.degree.
C. for a time period of from 10 minutes to 10 hours, preferably
from 20 minutes to 5 hours, and more preferably from 30 minutes to
3 hours at ambient, reduced or elevated pressure.
The group IVB transition metal included in the solid catalyst
component [A'] is a metal selected from the group consisting of
titanium, zirconium and hafnium. The transition metal included in
the solid catalyst component [A'] may preferably be titanium or
zirconium, and more preferably zirconium in the second embodiment
of the present invention.
Examples of the group IVB transition metal compound contained in
the solid catalyst component [A'] include zirconium, titanium and
hafnium compounds having a ligand including conjugated .pi.
electron as described for the catalyst component [A] in the first
embodiment of the present invention.
The group IVB transition metal compounds may be loaded on said
fine-particle carrier by allowing functional radicals on the
surface of the fine-particle carrier to react with said transition
metal compound; contacting said fine-particle carrier with said
transition metal compound after an optional preliminary contact
treatment of the carrier with the aforementioned organoaluminum
compound, aluminoxane compound or halogen-containing silane
compound; contacting the fine-particle carrier with the transition
metal compound in an inert hydrocarbon medium, and evaporating the
hydrocarbon medium to precipitate the transition metal compound
onto the carrier; contacting the fine-particle carrier with the
aluminoxane in an inert hydrocarbon medium, preparing an
aluminoxane-loaded fine-particle carrier by evaporating said medium
or by adding a solvent to which the aluminoxane is either insoluble
or hardly soluble to precipitate the aluminoxane onto the carrier,
and contacting the transition metal compound with the
aluminoxane-loaded fine-particle carrier to precipitate the
transition metal compound onto the carrier; contacting the
fine-particle carrier with the transition metal compound in an
inert hydrocarbon medium, and evaporating the hydrocarbon medium to
precipitate the transition metal compound onto the carrier; and
contacting the fine-particle carrier with the transition metal
compound in an inert hydrocarbon medium, and precipitating the
transition metal compound onto the fine-particle carrier by adding
a solvent to which the aluminoxane is either insoluble or hardly
soluble.
The catalyst component (B) is the same as the catalyst component
(B) as set forth in the first embodiment of the present
invention.
In the practice of the present invention, the aluminoxane (B) may
be supplied to the polymerization reaction system by methods as set
forth below.
(1) The solid catalyst component (A') is not loaded with the
aluminoxane. The solid catalyst component (A') and the aluminoxane
(B) are independently supplied to the polymerization reaction
system.
(2) The solid catalyst component (A') is the fine-particle carrier
loaded with the group IVB transition metal compound and the
aluminoxane (B). The solid catalyst component is supplied to the
polymerization reaction system.
(3) The solid catalyst component (A') is that of (2). The solid
catalyst component (A') is supplied to the polymerization reaction
system together with the aluminoxane (B).
The solid catalyst component (A') comprising the fine-particle
carrier loaded with the group IVB transition metal compound and the
aluminoxane (B) may be prepared by the following processes (a)
through (d) disclosed in Japanese Patent Application Nos. 61-311286
and 61-311287. (a) An olefin-polymerizing solid catalyst may be
prepared by contacting a suspension of the fine-particle carrier
dispersed in the aluminoxane solution with a solvent to which the
aluminoxane is either insoluble or hardly soluble to produce an
aluminoxane-loaded fine-particle carrier, and contacting said
aluminoxane-loaded fine-particle carrier with the transition metal
compound to produce a solid component.
Specifically, the olefin-polymerizing solid catalyst may be
prepared by adding the solvent to which the aluminoxane is either
insoluble or hardly soluble to the suspension comprising the
aluminoxane solution and the fine-particle carrier to precipitate
the aluminoxane onto the fine-particle carrier and form the
aluminoxane-loaded fine-particle carrier; and contacting the
suspension comprising the aluminoxane-loaded carrier and the
solvent to which the aluminoxane is either insoluble or hardly
soluble with the solution of the group IVB transition metal
compound to load the catalyst-component transition metal compound
onto the aluminoxane-loaded carrier. The aluminoxane may also be
precipitated by adding said suspension comprising the aluminoxane
solution and the carrier to the solvent to which the aluminoxane is
either insoluble or hardly soluble. The aluminoxane precipitation
may also be promoted by evaporating off the solvent used to
dissolve the aluminoxane from said mixed suspension.
In the step of contacting the suspension comprising the aluminoxane
solution and the fine-particle carrier with the solvent to which
the aluminoxane is either insoluble or hardly soluble, the
proportion of the solvent to which the aluminoxane is either
insoluble or hardly soluble may generally be in the range of from
10 to 10,000 parts by weight, and preferably from 100 to 1,000
parts by weight based on 100 parts by weight of the aluminoxane
solution. The contact treatment is generally carried out with
agitation at a temperature of from -100.degree. C. to 300.degree.
C., preferably from -50.degree. C. to 100.degree. C., and more
preferably from -30.degree. C. to 50.degree. C.
The aluminoxane solution is prepared at least from the aluminoxane
and the solvent capable of dissolving the aluminoxane as will be
exemplified later. The aluminoxane solution may be obtained by
simply mixing both compounds, or by mixing both compounds under
heating. The solvent included in the aluminoxane solution may
generally be from 0.1 to 50 liters, preferably from 0.2 to 10
liters, and more preferably from 0.3 to 2 liters per 1 gram atom of
aluminum in the aluminoxane.
The amount of the fine-particle carrier employed in the suspension
of the fine-particle carrier into the aluminoxane solution may
generally be in the range of from 1 to 500 g, preferably from 10 to
200 g, and more preferably from 20 to 100 g per liter of the
aluminoxane solution.
In the step of contacting the suspension of the aluminoxane-loaded
carrier with the transition metal compound, the transition metal
compound may be used in an amount of from 0.0005 to 1 mole,
preferably from 0.001 to 0.1 mole and more preferably from 0.002 to
0.04 mole per 1 gram atom of aluminum of the solid aluminoxane in
the suspension.
This contact treatment may generally be carried out with agitation
at a temperature in the range of from -50.degree. C. to 200.degree.
C., preferably from -20.degree. C. to 100.degree. C., and more
preferably from -10.degree. C. to 50.degree. C.
The solution of the transition metal compound is prepared at least
from the transition metal compound and the solvent used to dissolve
the transition metal compound as will be exemplified later. The
solution of the transition metal may be obtained by simply mixing
both compounds, or by mixing both compounds under heating. The
solvent included in the solution of the transition metal compound
may generally be from 1 to 500 liters, preferably from 2 to 200
liters, and more preferably from 3 to 100 liters per 1 mole of the
transition metal compound.
(b) An olefin-polymerizing solid catalyst may be prepared by
contacting a suspension of the fine-particle carrier dispersed into
a solution of the aluminoxane and the group IVB transition metal
with the solvent to which the aluminoxane is either insoluble or
hardly soluble to produce a solid component.
Specifically, the olefin-polymerizing solid catalyst may be
prepared by adding the solvent to which the aluminoxane is either
insoluble or hardly soluble to the suspension comprising the
aluminoxane, the transition metal compound, and the fine-particle
carrier to precipitate the aluminoxane and the transition metal
compound onto the carrier and form the fine-particle carrier loaded
with the aluminoxane and the transition metal compound. The
aluminoxane and the transition metal compound may also be
precipitated by adding the suspension comprising the aluminoxane,
the transition metal compound, and the fine-particle carrier to the
solvent to which the aluminoxane is either insoluble or hardly
soluble. The precipitation of the aluminoxane and/or the transition
metal compound may also be promoted by evaporating off the solvent
used for dissolving the aluminoxane from said mixed suspension.
In the step of contacting the suspension comprising the
fine-particle carrier and the solution of the aluminoxane and the
transition metal compound with the solvent to which the aluminoxane
is either insoluble or hardly soluble, the solvent to which the
aluminoxane is either insoluble or hardly soluble may generally be
used in a proportion in the range of from 10 to 10,000 parts by
weight, preferably from 100 to 1,000 parts by weight based on 100
parts by weight of the solution of the aluminoxane and the
transition metal compound. The contact treatment is generally
carried out with agitation at a temperature of from -100.degree. C.
to 300.degree. C., preferably from -50.degree. C. to 100.degree.
C., and more preferably from -30.degree. C. to 50.degree. C.
The solution of the aluminoxane and the transition metal compound
is prepared at least from the aluminoxane, the transition metal
compound and the solvent used for dissolving the aluminoxane as
will be exemplified later. The solution may be obtained by simply
mixing these compounds, or by mixing these compounds under heating.
The solvent included in the solution may generally be from 0.1 to
50 liters, preferably from 0.2 to 10 liters, and more preferably
from 0.3 to 2 liters per 1 gram atom aluminum in the
aluminoxane.
In the solution, the aluminoxane and the transition metal compound
may be included in a ratio of 0.0005 to 1, preferably 0.001 to 0.1,
and more preferably from 0.002 to 0.04 mole of the transition metal
compound per 1 gram atom of aluminum in the aluminoxane.
In the suspension of the fine-particle carrier dispersed in the
solution of the aluminoxane and the transition metal compound, the
amount of the carrier is from 1 to 500 g, preferably from 10 to 200
g, and more preferably from 20 to 100 g per 1 liter of the
solution.
The contact treatment may generally be carried out with agitation
at a temperature of from -100.degree. C. to 300.degree. C.,
preferably from -50.degree. to 100.degree. C., and more preferably
from -30.degree. to 50.degree. C.
(c) An olefin-polymerizing solid catalyst may be prepared by
contacting a suspension of the fine-particle carrier dispersed in
the solvent to which the aluminoxane is either insoluble or hardly
soluble with the aluminoxane solution to form a suspension of an
aluminoxane-loaded fine-particle carrier; and contacting the
aluminoxane-loaded carrier with the solution of the transition
metal compound to form a solid component.
Specifically, the olefin-polymerizing solid catalyst may be
prepared by adding the aluminoxane solution to the suspension of
the fine-particle carrier dispersed into the solvent to which the
aluminoxane is either insoluble or hardly soluble to precipitate
the aluminoxane onto the fine-particle carrier and form an
aluminoxane-loaded fine-particle carrier; and contacting the
suspension comprising the aluminoxane-loaded carrier and the
solvent to which the aluminoxane is either insoluble or hardly
soluble with the solution of the transition metal compound to
precipitate the catalyst-component transition metal compound onto
the aluminoxane-loaded carrier. The aluminoxane may also be
precipitated by adding the suspension comprising the fine-particle
carrier and the solvent to which the aluminoxane is either
insoluble or hardly soluble to the aluminoxane solution. The
aluminoxane precipitation may also be promoted by evaporating off
the solvent used for dissolving the aluminoxane from said mixed
suspension.
In the suspension comprising the fine-particle carrier and the
solvent to which the aluminoxane is either insoluble or hardly
soluble, the amount of the carrier may generally be from 1 to 500
g, preferably from 10 to 200 g, and more preferably from 20 to 100
g per 1 liter of the solvent. The step of contacting the suspension
with the aluminoxane solution may generally be carried out with
agitation at a temperature of from -100.degree. C. to 300.degree.
C., preferably from -50.degree. C. to 100.degree. C., and more
preferably from -30.degree. C. to 50.degree. C. In this step, the
amount of the aluminoxane solution may generally be in the range of
from 1 to 1,000 parts by weight, preferably from 10 to 100 parts by
weight based on 100 parts by weight of the suspension.
The aluminoxane solution is prepared at least from the aluminoxane
and the solvent capable of dissolving the aluminoxane as will be
exemplified later. The aluminoxane solution may be obtained by
simply mixing both compounds, or by mixing both compounds under
heating. The solvent included in the aluminoxane solution may
generally be from 0.1 to 50 liters, preferably from 0.2 to 10
liters, and more preferably from 0.3 to 2 liters per 1 gram atom of
aluminum in the aluminoxane.
In the step of contacting the aluminoxane-loaded fine-particle
carrier with the solution of the transition metal compound, the
transition metal compound may be used in an amount of 0.0005 to 1
mole, preferably from 0.001 to 0.1 mole, and more preferably from
0.002 to 0.04 mole per 1 gram atom of aluminum in the
aluminum-loaded carrier.
This step may generally carried out with agitation at a temperature
of from -50.degree. C. to 200.degree. C., preferably from
-20.degree. C. to 100.degree. C., and more preferably from
-10.degree. C. to 50.degree. C.
The solution of the transition metal compound is prepared at least
from the transition metal compound and the solvent used for
dissolving the transition metal compound as will be exemplified
later. The transition metal compound solution may be obtained by
simply mixing both compounds, or by mixing both compounds under
heating. The solvent included in the solution of the transition
metal compound may generally be from 1 to 500 liters, preferably
from 2 to 200 liters, and more preferably from 3 to 100 liters per
1 mole of the transition metal compound.
(d) An olefin-polymerizing solid catalyst may be prepared by
contacting a suspension of the fine-particle carrier dispersed in
the solvent to which the aluminoxane is either insoluble or hardly
soluble with the solution of the aluminoxane and the group IVB
transition metal compound to precipitate the aluminoxane and the
transition metal compound onto the fine-particle carrier and form a
solid component.
Specifically, the olefin-polymerizing solid catalyst may be
prepared by adding the solution of the aluminoxane and the
transition metal to the suspension of the fine-particle carrier
dispersed in the solvent to which the aluminoxane is either
insoluble or hardly soluble to precipitate the aluminoxane and the
group VIB transition metal compound onto the fine-particle carrier
and produce a fine-particle carrier loaded with the aluminoxane and
the transition metal catalyst. The aluminoxane and the transition
metal compound may also be precipitated by adding the suspension
comprising the fine-particle carrier and the solvent to which the
aluminoxane is either insoluble or hardly soluble to the solution
of the aluminoxane and the group IVB transition metal compound. The
precipitation of the aluminoxane and/or the transition metal
compound may also be promoted by evaporating off the solvent used
for dissolving the aluminoxane and the transition metal compound
from said mixed suspension.
In the suspension comprising the fine-particle carrier and the
solvent to which the aluminoxane is either insoluble or hardly
soluble, the amount of the carrier may generally be from 1 to 500
g, preferably from 10 to 200 g, and more preferably from 20 to 100
g per 1 liter of the solvent. The step of contacting the suspension
with the solution of the aluminoxane and the transition metal
compound may generally be carried out with agitation at a
temperature of from -100.degree. C. to 300.degree. C., preferably
from -50.degree. C. to 100.degree. C., and more preferably from
-30.degree. C. to 50.degree. C. In this step, the amount of the
solution of the aluminoxane and the transition metal compound may
generally be in the range of from 1 to 1,000 parts by weight, and
preferably from 10 to 100 parts by weight based on 100 parts by
weight of the suspension.
The solution of the aluminoxane and the transition metal compound
is prepared at least from the aluminoxane, the transition metal
compound and the solvent used for dissolving the aluminoxane as
will be exemplified later. The solution may be obtained by simply
mixing these compounds, or by mixing these compounds under heating.
The solvent included in the solution may generally be from 0.1 to
50 liters, preferably from 0.2 to 10 liters, and more preferably
from 0.3 to 2 liters per 1 gram atom of aluminum in the
aluminoxane.
The amount of the transition metal compound in the solution may
generally be from 0.0005 to 1 mole, preferably from 0.001 to 0.1
mole, and more preferably from 0.002 to 0.04 mole per 1 mole of the
aluminum atom.
The solvents which are capable of dissolving the group IVB
transition metal compound include, aromatic hydrocarbons such as
benzene, toluene, ethylbenzene, propylbenzene, butylbenzene, and
xylene, and halogen-containing hydrocarbons such as chlorobenzene
and dichloroethane.
The solvents to which the group IVB transition metal compound is
either insoluble or hardly soluble include aliphatic hydrocarbons
such as pentane, hexane, decane, dodecane, and kerosin, and
alicyclic hydrocarbons such as cyclohexane.
The solvents which are capable of dissolving the aluminoxane
include, aromatic hydrocarbons such as benzene, toluene,
ethylbenzene, propylbenzene, butylbenzene, and xylene.
The solvents to which the aluminoxane is either insoluble or hardly
soluble include linear and branched aliphatic hydrocarbons such as
pentane, hexane, decane, dodecane, and kerosin, and alicyclic
hydrocarbons such as cyclohexane, norbornane, and
ethylcyclohexane.
The solvent to which the aluminoxane is either insoluble or hardly
soluble may preferably have a higher boiling point than the solvent
used for dissolving the aluminoxane.
The solid catalyst component (A') prepared by the processes as set
forth above may contain the transition metal compound in an amount
of from 0.5 to 500 mg atoms, preferably from 1 to 200 mg atoms, and
more preferably from 3 to 50 mg atoms calculated as transition
metal atom per 100 g of the fine-particle carrier. The
catalyst-component (B) may contain the aluminoxane in an amount of
from 5 to 50,000 mg atoms, preferably from 50 to 10,000 mg atoms,
and more preferably from 100 to 4,000 mg atoms calculated as
aluminum atom per 100 g of the organic fine-particle carrier. In
the solid catalyst component (A'), the atomic ratio (Al/M) of the
transition metal to aluminum may be from 1 to 1,000, preferably
from 6 to 600, and more preferably from 15 to 300, and the average
particle diameter may be from 5 to 200 .mu.m, preferably from 10 to
150 .mu.m, and more preferably from 20 to 100 .mu.m.
The polymerization process of the present invention is effective
for preparing an olefin polymer, particularly, ethylene polymer and
an ethylene-a-olefin copolymer. Examples of the olefins which can
be polymerized by the catalyst of the present invention include
a-olefins having 2 to 20 carbon atoms, such as ethylene, propylene,
1-butene, 1-hexene, 4-methyl-1-pentene, 1-octene, 1-decene,
1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-eicocene,
etc. Among these, the present invention is suitable for
polymerizing ethylene, or copolymerizing ethylene with an a-olefin
having 3 to 10 carbon atoms.
In an olefin polymerization according to the present invention,
olefins are polymerized by a gas-phase polymerization or a
liquid-phase polymerization such as slurry polymerization. In the
slurry polymerization, either an inert hydrocarbon or the olefin
itself may be used as a solvent.
Illustrative hydrocarbon media are aliphatic hydrocarbons such as
butane, isobutane, pentane, hexane, octane, decane, dodecane,
hexadecane, octadecane, etc.; alicyclic hydrocarbons such as
cyclopentane, methylcyclopentane, cyclohexane, cyclooctane, etc.;
and petroleum cuts such as kerosine, gas oil, etc.
The amount of the transition metal compound used in the
liquid-phase polymerization including the slurry polymerization or
the gas-phase polymerization according to the present method may
generally be in the range of 10.sup.-8 to 10.sup.-2 gram
atoms/liter, and preferably 10.sup.-7 to 10.sup.-3 gram atoms/liter
as a concentration of the transition metal atom in the
polymerization system.
The amount of the aluminoxane used in the liquid-phase or gas-phase
polymerization according to the present invention may generally be
up to 6 mg atoms/liter, preferably up to 3 mg atoms/liter, more
preferably from 0.01 to 2 mg atoms/liter, and most preferably from
0.02 to 1 mg atom/liter. The ratio of aluminum atoms contained in
the aluminoxane component (B) to the sum of the aluminum atoms
contained in the aluminoxane component (B) and the organoaluminum
compound component (C) may generally be from 20 to 95%, and
preferably from 40 to 92%. The ratio of aluminum atoms contained in
the the organoaluminum compound component (C) to the sum of the
aluminum atoms contained in the aluminoxane component (B) and the
organoaluminum compound component (C) may generally be from 5 to
80%, and preferably from 8 to 60%. In the process according to the
present invention, the ratio of the sum of the aluminum atoms
contained in the aluminoxane component (B) and the organoaluminum
compound component (C) to the transition metal atoms in the
reaction system may generally be from 20 to 10,000, preferably from
40 to 5,000, and more preferably from 60 to 2,000.
When the process of the present invention is carried out by a
liquid-phase polymerization such as slurry polymerization, the
polymerization temperature may generally be in the range of from
-50.degree. C. to 120.degree. C., and preferably from 0.degree. C.
to 100.degree. C.
When the process of the present invention is carried out by a
gas-phase polymerization, the polymerization temperature may
generally be in the range of from 0.degree. C. to 120.degree. C.,
and preferably from 20.degree. C. to 100.degree. C.
The olefin polymerization may generally be carried out under a
pressure of standard pressure to 100 kg/cm.sup.2, and preferably
from 2 to 50 kg/cm.sup.2 by a batch method, semi-continuous method,
or continuous method.
Further, the polymerization may be carried out in two or more steps
corresponding to different reaction conditions.
When the slurry polymerization or the gas-phase polymerization is
employed herein, a preliminary polymerization of the olefin may
preferably be carried out prior to the olefin polymerization in the
presence of above-mentioned catalyst. In the preliminary
polymerization, from 1 to 1,000 g, preferably 5 to 500 g, and more
preferably from 10 to 200 g of the olefin is polymerized per 1 gram
atom of the transition metal component, namely the catalyst
component (A). Examples of the olefins used for the preliminary
polymerization besides ethylene include a-olefins having 3 to 20
carbon atoms such as propylene, 1-butene, 4-methyl-1-pentene,
1-hexene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene. Ethylene
is preferred.
The preliminary polymerization may be carried out at a temperature
of from -20.degree. C. to 70.degree. C., preferably from
-10.degree. C. to 60.degree. C., and more preferably from 0.degree.
C. to 50.degree. C.
The preliminary polymerization may be carried out either by a batch
method or by a continuous method, and either under an atmospheric
pressure or under an elevated pressure.
The preliminary polymerization may be carried out in the presence
of a molecular weight modifier such as hydrogen. The molecular
weight modifier may preferably be used in an amount sufficient to
prepare a preliminarily polymerized product having an intrinsic
viscosity .eta. of at least 0.2 dl/g, and preferably from 0.5 to 20
dl/g.
The preliminary polymerization may be carried out without using any
solvent or in an inert hydrocarbon medium, and preferably in an
inert hydrocarbon medium. The inert hydrocarbon medium used in the
preliminary polymerization may be selected from the above-described
solvents to which the aluminoxane is either insoluble or hardly
soluble.
In the preliminary polymerization, the catalyst concentration
within the reaction system may generally be in the range of from
10.sup.-6 to 1 gram atom/liter, and preferably from 10.sup.-4 to
10.sup.-2 gram atom/liter.
EXAMPLE
The present invention is hereinafter illustratively described by
referring to the examples.
Preparation of methylaluminoxane
A 400 ml flask equipped with an agitator was fully purged with
nitrogen and charged with 37 g of Al.sub.2
(SO.sub.4).sub.3.14H.sub.2 O and 125 ml of toluene, and cooled to
0.degree. C. To this solution, 125 ml toluene solution containing
50 ml trimethylaluminum was added dropwise in 1 hour. The solution
was then gradually heated to 40.degree. C. in 2 hours, and reacted
at this temperature for 40 hours. After the reaction, solid was
removed by filtration, and low-boiling contents were removed from
the filtrate by means of an evaporator. Toluene was added to the
remaining viscous solution to obtain the methylaluminoxane as a
toluene solution.
The molecular weight determined by cryoscopy in benzene was 888.
Accordingly, the degree of polymerization of this aluminoxane was
15.
EXAMPLE 1
A 1 liter glass reactor fully purged with nitrogen was charged with
350 ml of toluene and 150 ml of 4-methyl-1-pentene. To the reaction
system, 0.38 mmol of pentene. To the reaction system, 0.38 mmol of
diisobutylaluminum methoxide, 0.75 mmol calculated as Al atom of
the methylaluminoxane in toluene, and 0.0025 mmol calculated as Zr
atom of biscyclopentadienylzirconium dichloride in toluene was
respectively added while ethylene was introduced at a rate of 155
Nl/hr. The reaction solution was adjusted to a temperature of
20.degree. C. by means of an ice water. When 5 minutes had passed
after the addition of biscyclopentadienylzirconium dichloride,
about 5 ml of methanol was added to stop the polymerization. The
resulting polymer was thoroughly dried, and the yield was measured
to be 14.8 g.
EXAMPLES 2-4
The procedure of Example 1 was repeated except that 0.38 mmol
diisobutylaluminum methoxide employed in Example 1 was replaced by
the compounds shown in Table 1. The results are also shown in Table
1.
Comparative Example 1
The procedure of Example 1 was repeated except that the use of
diisobutylaluminum methoxide was omitted. The results are shown in
Table 1.
TABLE 1
__________________________________________________________________________
Methyl- Polymerization Organoaluminum aluminoxane, activity, MFI,
Density, Example compound, mM mM* gPE/mMZr dg/min g/min
__________________________________________________________________________
1 (isoBu).sub.2 AlOMe 0.38 0.75 5900 1.7 0.881 2 (isoBu).sub.2
AlOMe 0.075 0.75 4200 1.8 0.883 3 (isoBu).sub.2 AlOSiMe.sub.3 0.38
0.75 5200 2.2 0.877 4 (isoBu).sub.2 Al(SiEt).sub.3 0.38 0.75 5700
1.8 0.882 1** -- 0 0.75 1660 3.6 0.886
__________________________________________________________________________
*calculated as aluminum atom. **comparative example.
EXAMPLE 5
Preparation of solid catalyst
To a 300 ml pressure-reducible reactor equipped with an agitator,
67 ml of toluene solution containing 100 mmol calculated as
aluminum atom of said methylaluminoxane was added, and 100 ml of
purified n-decane was then gradually added for about 0.5 hour at
room temperature with agitation to precipitate the
methylaluminoxane. The reactor was evacuated to a pressure of 4
torr by means of a vacuum pump while the temperature of the reactor
was gradually elevated to 35.degree. C. in about 3 hours to remove
toluene within the reactor and further precipitate the
methylaluminoxane. The reaction solution was filtered to remove the
liquid-phase portion. The thus obtained solid portion was further
suspended in n-decane, to which 5 ml toluene solution containing
0.2 mmol biscyclopentadienylzirconium dichloride was added. After
stirring at room temperature for about 1 hour, the reaction
solution was subjected to a filtration to remove liquid-phase
portion and obtain an olefin-polymerizing solid catalyst.
The thus obtained solid catalyst had a Zr content of 0.6% by
weight, Al content of 47% by weight, and average catalyst-particle
diameter measured by microscope observation of about 30 .mu.m.
Preliminary polymerization
To a 400 ml reactor equipped with an agitator, 100 ml of purified
n-decane, 50 mmol of diisobutylaluminum methoxide, and 0.1 mmol
calculated as Zr of said solid catalyst was added under nitrogen
atmosphere. Ethylene was introduced into the reaction system at a
rate of 4 Nl/hr for 1 hour, while the temperature was kept at
20.degree. C. After completing the ethylene introduction, the
reaction system was purged with nitrogen, washed once with purified
hexane, and further suspended in hexane and stored in a catalyst
bottle.
Polymerization
An autoclave having an internal volume of 2 liters was fully purged
with nitrogen and charged with a dispersant of 250 g sodium
chloride. The autoclave was evacuated with a vacuum pump to an
internal pressure of 50 mmHg or less at an elevated temperature of
90.degree. C. for 2 hours. The autoclave was cooled to a
temperature of 75.degree. C., purged with ethylene, and charged
with 0.005 mmol calculated as zirconium atom of the preliminarily
treated solid catalyst component. The autoclave was sealed and then
charged with 50 Nml of hydrogen, and the internal pressure was then
elevated to 8 kg/cm.sup.2 G with ethylene. The agitation speed was
increased to 300 rpm and the polymerization was carried out at
80.degree. C. for 1 hour.
After completing the polymerization, the polymer and the sodium
chloride within the autoclave were all taken out and introduced
into about 1 liter of water. After 5 minutes of agitation,
substantially all of the sodium chloride dissolved in water, and
only the polymer was floating on the water. The floating polymer
was recovered, thoroughly washed with methanol, and dried overnight
at 80.degree. C. under reduced pressure. The results are shown in
Table 2.
Comparative Example 2
The procedure of Example 5 was repeated except that
diisobutylaluminum methoxide was not employed. The results are
shown in Table 2.
EXAMPLE 6
The procedure of Example 5 was repeated except that
diisobutylaluminum methoxide was replaced by isoBu.sub.2
AlOSiEt.sub.3. The results are shown in Table 2.
TABLE 2 ______________________________________ Polymerization MFI,
Apparent bulk Example activity, gPE/mMZr dg/min density, g/ml
______________________________________ 5 21,700 1.1 0.45 6 18,900
2.1 0.45 2* 13,300 6.2 0.45 ______________________________________
*comparative example
EXAMPLE 7
Preparation of solid catalyst loaded on a carrier
To a 300 ml pressure-reducable reactor equipped with an agitator,
67 ml of toluene solution containing 100 mmol calculated as
aluminum atom of said methylaluminoxane and 4 g of powder
polyethylene having an average particle diameter of 35 .mu.m (trade
name Mipelon.RTM., manufactured by Mitsui Petrochemical Industries
Ltd.) were added. Reaction system was kept at room temperature and
100 ml of purified n-decane was gradually added in about 0.5 hour
with agitation to precipitate the methylaluminoxane. The reactor
was then evacuated to a pressure of 4 torr by means of a vacuum
pump while the temperature of the reactor was gradually elevated to
45.degree. C. in about 3 hours to remove toluene within the reactor
and further precipitate the methylaluminoxane. The reaction
solution was filtered to remove the liquid-phase portion. The thus
obtained solid portion was further suspended in n-decane, to which
5 ml toluene solution containing 0.24 mmol
biscyclopentadienylzirconium dichloride was added. After stirring
at room temperature for about 1 hour, the reactor was evacuated to
about 4 torr for 30 minutes at room temperature to remove toluene.
To the suspension, 10 mmol of diisobutylaluminum methoxide was
added and stirred for 60 minutes at room temperature. The reaction
solution was cooled to -20.degree. C., and filtered to obtain an
olefin-polymerizing solid catalyst.
The thus obtained solid catalyst had a Zr content per 100 g carrier
polyethylene of 10 mmol, Al content per 100 g carrier polyethylene
of 2.2 mol, and average catalyst-particle diameter measured by
microscope observation of about 40 .mu.m.
Preliminary polymerization
To a 400 ml reactor equipped with an agitator, 100 ml of purified
n-decane and 0.1 mmol calculated as Zr of said solid catalyst was
added under nitrogen atmosphere. Ethylene was introduced into the
reaction system at a rate of 4 Nl/hr for 1 hour, while the
temperature was kept at 20.degree. C. After completing the ethylene
introduction, the reaction system was purged with nitrogen, washed
once with purified hexane, and further suspended in hexane and
stored in a catalyst bottle.
Polymerization
An autoclave having an internal volume of 2 liters was fully purged
with nitrogen and charged with a dispersant of 250 g sodium
chloride. The autoclave was evacuated with a vacuum pump to an
internal pressure of 50 mmHg or less at an elevated temperature of
90.degree. C. for 2 hours. The autoclave was cooled to a
temperature of 75.degree. C., purged with ethylene, and charged
with 0.005 mmol calculated as zirconium atom of the preliminarily
treated solid catalyst component. The autoclave was sealed and then
charged with 50 Nml of hydrogen, and the internal pressure was then
elevated to 8 kg/cm.sup.2 G with ethylene. The agitation speed was
increased to 300 rpm and the polymerization was carried out at
80.degree. C. for 1 hour.
After completing the polymerization, the polymer and the sodium
chloride within the autoclave were all taken out and introduced
into about 1 liter of water. After 5 minutes of agitation,
substantially all of the sodium chloride dissolved in water, and
only the polymer was floating on the water. The floating polymer
was recovered, thoroughly washed with methanol, and dried overnight
at 80.degree. C. under reduced pressure. The resulting polymer had
an yield of 103 g, MFR of 1.4 dg/min, and apparent bulk density of
0.45 g/ml.
Comparative Example 3
The procedure of Example 7 was repeated except that
diisobutylaluminum methoxide was not employed. The results are
shown in Table 3.
EXAMPLE 8
Preparation of solid catalyst loaded on a carrier
To a 300 ml pressure-reducible reactor equipped with an agitator,
67 ml of toluene solution containing 100 mmol calculated as Al atom
of said methylaluminoxane and 4 g of powder polyethylene having an
average particle diameter of 35 .mu.m (trade name Mipelon.RTM.,
manufactured by Mitsui Petrochemical Industries Ltd.) were added.
Reaction system was kept at room temperature and 100 ml of purified
n-decane was gradually added in about 0.5 hour with agitation to
precipitate the methylaluminoxane. The reactor was then evacuated
to a pressure of 4 torr by means of a vacuum pump while the
temperature of the reactor was gradually elevated to 45.degree. C.
in about 3 hours to remove toluene within the reactor and further
precipitate the methylaluminoxane. The reaction solution was
filtered to remove the liquid-phase portion. The thus obtained
solid portion was further suspended in n-decane, to which 5 ml
toluene solution containing 0.24 mmol biscyclopentadienylzirconium
dichloride was added. After stirring at room temperature for about
1 hour, the reactor was evacuated to about 4 torr for 30 minutes at
room temperature to remove toluene. The suspension was filtered to
obtain an olefin-polymerizing solid catalyst.
The thus obtained solid catalyst had a Zr content per 100 g carrier
polyethylene of 10 mmol, Al content per 100 g carrier polyethylene
of 1.9 mol, and average catalyst-particle diameter measured by
microscope observation of about 40 .mu.m.
Preliminary polymerization
To a 400 ml reactor equipped with an agitator, 100 ml of purified
n-decane, 50 mmol of diisobutylaluminum methoxide, and 0.1 mmol
calculated as Zr of said solid catalyst was added under nitrogen
atmosphere. Ethylene was introduced into the reaction system at a
rate of 4 Nl/hr for 1 hour, while the temperature was kept at
20.degree. C. After completing the ethylene introduction, the
reaction system was purged with nitrogen, washed once with purified
hexane, and further suspended in hexane and stored in a catalyst
bottle.
Polymerization
Ethylene was polymerized in a similar manner as Example 7.
Comparative Example 4
The procedure of Example 8 was repeated except that
diisobutylaluminum methoxide was not employed. The results are
shown in Table 3.
EXAMPLE 9
Preparation of solid catalyst loaded on a carrier
To a 300 ml pressure-reducible reactor equipped with an agitator,
67 ml of toluene solution containing 100 mmol calculated as Al atom
of said methylaluminoxane and 2 g of silica which had been calcined
at 500.degree. C. for 12 hours (#952, prepared by Devison K.K.)
were added. Reaction system was kept at room temperature and 100 ml
of purified n-decane was gradually added in about 0.5 hour with
agitation to precipitate the methylaluminoxane. The reactor was
then evacuated to a pressure of 4 torr by means of a vacuum pump
while the temperature of the reactor was gradually elevated to
35.degree. C. in about 3 hours to remove toluene within the reactor
and further precipitate the methylaluminoxane. The reaction
solution was filtered to remove the liquid-phase portion. The thus
obtained solid portion was further suspended in n-decane, to which
5 ml toluene solution containing 0.2 mmol
biscyclopentadienylzirconium dichloride was added. After stirring
at room temperature for about 1 hour, liquid-phase portion was
removed to obtain an olefin-polymerizing solid catalyst.
The thus obtained solid catalyst had a Zr content per 100 g carrier
polyethylene of 7 mmol, Al content per 100 g carrier polyethylene
of 2.4 mol, and average catalyst-particle diameter measured by
microscope observation of about 40 .mu.m.
The preliminary polymerization and the solventlesspolymerization of
ethylene were carried out in a similar manner as Example 8. The
results are shown in Table 3.
Comparative Example 5
The procedure of Example 9 was repeated except that
diisobutylaluminum methoxide was not employed. The results are
shown in Table 3.
TABLE 3 ______________________________________ Polymerization MFI,
Apparent bulk Example activity, gPE/mMZr dg/min density, g/ml
______________________________________ 7 20,600 1.4 0.45 3* 14,300
3.3 0.45 8 21,300 1.1 0.46 4* 14,300 3.3 0.45 9 19,700 1.7 0.45 5*
13,200 6.2 0.46 ______________________________________ *comparative
example
Preparation of aluminoxane
A 400 ml flask was fully purged with nitrogen and charged with 37 g
of Al.sub.2 (SO.sub.4).sub.3.14H.sub.2 O and 125 ml of toluene, and
cooled to 0.degree. C. To this solution, 500 mmol trimethylaluminum
diluted with 125 ml toluene solution was added dropwise. The
solution was then heated to 40.degree. C. and allowed to react for
10 hours at this temperature. After the reaction, solid was removed
by filtration, and toluene was further removed from the filtrate to
give 13 g of aluminoxane as a white solid.
The molecular weight determined by cryoscopy in benzene was 930.
Accordingly, the value of m (degree of polymerization) in the
catalyst component (B) was 14.
EXAMPLE 10
Preparation of solid catalyst loaded on a carrier
To a 200 ml flask fully purged with nitrogen, 52 g of silica having
average particle diameter of 70 .mu.m, specific surface area of 260
m.sup.2 /g, and pore volume of 1.65 cm.sup.3 /g which had been
calcined for 5 hours, 26 ml of toluene solution of dimethylaluminum
monochloride (Al, 1 mol/liter), and 50 ml of toluene were added and
heated at 80.degree. C. for 2 hours. Solid portion was separated by
filtration to obtain catalyst component. The thus obtained catalyst
component was transferred into 50 ml of toluene, and 43 ml toluene
solution of biscyclopentadienylzirconium dichloride (Zr, 0.04
mol/liter) which is a catalyst component was added thereto. The
reaction mixture was heated at 80.degree. C. for 1 hour and
subjected to a filtration. To the thus obtained solid portion, 19.6
ml toluene solution of aluminoxane (Al, 1.03 mol/liter) and 80 ml
of toluene was added and the mixture was agitated for 30 minutes at
room temperature. Toluene was removed at room temperature by means
of an evaporator to give a solid catalyst having Zr content of
0.08% by weight and Al content of 10% by weight.
The preliminary polymerization and the solventless polymerization
of ethylene was carried out in a similar manner as Example 8 except
that the scale of the preliminary polymerization was reduced to one
half of the Example 8.
Comparative Example 6
The procedure of Example 10 was repeated except that
diisobutylaluminum methoxide was not employed. The results are
shown in Table 4.
EXAMPLE 11
Preparation of solid catalyst loaded on a carrier
A 400 ml pressure-reducible reactor equipped with an agitator was
fully purged with nitrogen. In this reactor, 50 ml toluene solution
containing 2 mmol aluminoxane was added to a suspension comprising
5 g of silica (#952, manufactured by Devison K.K.) calcined at
800.degree. C. for 12 hours and 100 ml of toluene at room
temperature. The mixed solution was heated to 50.degree. C. and
allowed to react for 2 hours at this temperature. When the reaction
had ceased, liquid portion was removed from the reaction solution
by filtration. The solid residue was suspended in 100 ml toluene,
and 9.4 ml toluene containing 0.38 mmol
biscyclopentadienylzirconium dichloride was added to the suspension
at 25.degree. C. The reaction was allowed to continue at this
temperature for 2 hours with agitation. When the reaction had
ceased, liquid portion was removed from the suspension by
filtration, and the solid residue was washed twice with toluene to
give the solid catalyst component (A') which had zirconium loading
weight of 0.6% by weight. To a 2 g portion of the thus obtained
solid catalyst component (A'), 47 ml toluene solution of
aluminoxane (Al, 1.03 mol/liter) and 50 ml toluene was added and
agitation was continued at room temperature for 30 minutes. Toluene
was then removed from the reaction system at room temperature by
means of an evaporator to give the aluminoxane-loaded solid
component.
The preliminary polymerization and the solventless polymerization
were then carried out in a manner similar to Example 8. The results
are shown in Table 4.
Comparative Example 7
The procedure of Example 11 was repeated except for that
diisobutylaluminum methoxide was not used. The results are shown in
Table 4.
EXAMPLE 12
Preparation of solid catalyst component (A')
A 400 ml pressure-reducible reactor equipped with an agitator was
fully purged with nitrogen. In this reactor, a mixed suspension
comprising 3 g of silica (#952, manufactured by Devison K.K.) which
had been calcined at 800.degree. C. for 12 hours and 50 ml of
trichlorosilane were reacted at 50.degree. C. for 2 hours with
agitation. When the reaction had ceased, liquid portion was removed
from the reaction solution by filtration. The solid residue was
suspended in 50 ml toluene, and 300 ml toluene containing 15 mmol
biscyclopentadienylzirconium dichloride was added to the suspension
at 25.degree. C. The reaction was allowed to continue at 50.degree.
C. for 2 hours with agitation. When the reaction had ceased, liquid
portion was removed from the suspension by filtration, and the
solid residue was washed twice with toluene to give the solid
catalyst component (A') which had zirconium loading weight of 1.2%
by weight. To a 1 g portion of the thus obtained solid catalyst
component (A'), 47 ml toluene solution of aluminoxane (Al, 1.03
mol/liter) and 50 ml toluene were added and agitation was continued
at room temperature for 30 minutes. Toluene was then removed from
the reaction system at room temperature by means of an evaporator
to give the aluminoxane-loaded solid component.
The preliminary polymerization and the solventless polymerization
were then carried out in a manner similar to Example 8. The results
are shown in Table 4.
Comparative Example 8
The procedure of Example 12 was repeated except that
diisobutylaluminum methoxide was not used. The results are shown in
Table 4.
TABLE 4 ______________________________________ Polymerization MFI,
Apparent bulk Example activity, gPE/mMZr dg/min density, g/ml
______________________________________ 10 7,200 0.8 0.39 6* 3,400
3.2 0.38 11 7,100 1.7 0.42 7* 4,100 6.3 0.42 12 5,100 1.8 0.41 8*
2,200 3.6 0.41 ______________________________________ *comparative
example
EXAMPLE 13
The procedure of Example 8 was repeated to prepare a solid catalyst
loaded on a carrier except that the amount of the methylaluminoxane
used was changed from 100 mmol to 30 mmol, and the amount of the
diisobutylaluminum methoxide added during the preliminary
polymerization was changed from 50 mmol to 15 mmol. The preliminary
polymerization and the solventless polymerization of ethylene were
also carried out in a similar manner as Example 8. The results are
shown in Table 5.
Comparative Example 9
The procedure of Example 13 was repeated except that
diisobutylaluminum methoxide was not used. The results are shown in
Table 5.
EXAMPLE 14
The procedure of Example 13 was repeated except that
diisobutylaluminum methoxide was replaced with (isoBu).sub.2
Al-O-SiEt.sub.3.
The results are shown in Table 5.
Comparative Example 10
The procedure of Example 14 was repeated except that (isoBu).sub.2
Al-O-SiEt.sub.3 was not used. The results are shown in Table 5.
TABLE 5 ______________________________________ Polymerization MFI,
Apparent bulk Example activity, gPE/mMZr dg/min density, g/ml
______________________________________ 13 7,100 1.4 0.45 9* 2,700
6.7 0.45 14 6,800 1.1 0.45 10* 2,700 6.7 0.45
______________________________________ *comparative example
INDUSTRIAL APPLICABILITY
The first embodiment of the present invention is directed to a
novel catalyst and a process for polymerizing an olefin by using
such a catalyst, which enables production of a homopolymer having a
narrow molecular-weight distribution as well as a copolymer having
a narrow composition distribution at a high polymerization
activity, even when the amount of aluminoxane included in the
catalyst is significantly reduced, by making use of synergistic
effects of aluminoxane and organoaluminum compound.
By utilizing the catalyst and the process for polymerizing the
olefin by using such a catalyst according to the second embodiment
of the present invention, production of a polymer and copolymer has
been enabled which has a high bulk density and uniform particle
size with little powdery product as well as the above-described
advantages.
* * * * *